EP0346996A2 - Process for preparing organic glasses - Google Patents
Process for preparing organic glasses Download PDFInfo
- Publication number
- EP0346996A2 EP0346996A2 EP89201532A EP89201532A EP0346996A2 EP 0346996 A2 EP0346996 A2 EP 0346996A2 EP 89201532 A EP89201532 A EP 89201532A EP 89201532 A EP89201532 A EP 89201532A EP 0346996 A2 EP0346996 A2 EP 0346996A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- weight
- allyl carbonate
- process according
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/24—Esters of carbonic or haloformic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
- C08L67/07—Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
- The present invention relates to a process for preparing organic glasses by means of the polymerization of a liquid composition containing at least one di-(allyl carbonate) or poly-(allyl carbonate) of a diol or polyol.
- Among the allyl carbonate monomers, bis-(allyl carbonate) of diethylene glycol, polymerized in the form of a thermosetting resin, is the one which was most successful and which asserted itself in applications at the industrial level in the preparation of organic glasses and optical articles endowed with particularly high optical and mechanical characteristics (F. Strain, "Encyclopaedia of Chemical Processing and Design", Vol. I, Interscience Publishers, New York, 1964, pages 799-foll.).
- In the industrial practice the optical articles obtained from this material, such as corrective ophthalmic lenses or sun glasses, shields, protective masks, and so forth, are endowed with extremely good characteristics of transparence, absence of colour, abrasion resistance, resistance to solvents and to ageing. Said optical articles are normally produced by polymerizing the monomer inside a mould (casting process), with the preliminary addition of a polymerization initiator of peroxy type.
- The polymerization is normally carried out in an oven, or in a water bath, within times ranging from about ten hours up to more tens of hours, depending on the optical article which is being produced, and following a suitable temperature profile. The long polymerization time constitutes the main limit of the process, in that it has a great influence on the economy of the process, and reduces the productivity. This explains the limited use, or the non-use of the material in question in large consume sectors, such as the automobile sector, the sector of glasses for the building industry, and the like, in spite of its excellent optical and mechanical features.
- U.S. patent No. 4,521.577 discloses liquid compositions comprising allyl carbonate monomers, polymerizable by a radicalic route to yield organic glasses. These compositions require hardening times comprised within the range of from 3 to 100 hours.
- European Pat. Appln. Publ. No. 0227178 discloses liquid compositions comprising allyl carbonate monomers, polymerizable by a radicalic route to yield organic glasses. These compositions require hardening times comprised within the range of from 1 to 5 hours.
- In U.K. patent application No. 2,171,709, a liquid composition containing diethylene-glycol bis-(allyl carbonate) and up to 40% by weight of a vinyl ester is hardened with a peroxide through a prepolymerization step, followed by a step of true polymerization. In Example 1 of this patent.application, the true polymerization step requires a time of 8 hours.
- The present Applicant has found now that the liquid compositions which contain one or more allyl carbonate monomers and a photoinitiator in combination with limited amounts of a vinyl monomer and/or with an organic peroxide can be polymerized producing completely hardened organic glasses or surface coatings within a time not higher than about 15 minutes.
- In accordance therewith, the present invention relates to a process for preparing organic glasses or surface coatings by means of the polymerization of a composition containing at least one allyl carbonate monomer, said process being characterized in that a polymerizable liquid composition which contains:
- (a) at least one bis-(allyl carbonate) or poly-(allyl carbonate) of respectively a diol or polyol;
- (b) a vinyl ester, with a weight ratio of said (a) component to said (b) component comprised within the range of from 100:0 to 70:30;
- (c) an organic peroxide in an amount comprised within the range of from 0 to 5 parts by weight per each 100 parts by weight of the total of (a) and (b) components; and
- (d) an organic photoinitiator in an amount comprised within the range of from 0.5 to 5 parts by weight per each 100 parts by weight of the total of (a) and (b) components, under the proviso that the (b) and (c) components are not simultaneously absent, is submitted to the action of U.V. light.
- In the preferred form of practical embodiment, both of said (b) and (c) components will be present.
- The composition can also additionally contain small amounts of an (e) component, selected from among those used, in the art in order to stabilize the organic polymers to the degrading action of U.V. light.
- In the preferred form of practical embodiment the polymerizable' liquid composition is heated to a temperature higher than room temperature before being submitted to the action of U.V. light.
- The (a) component of the composition is a bis-(allyl carbonate) or poly-(allyl carbonate) respectively of a diol or of a polyol. Useful for the intended purpose are the bis-(allyl carbonates) of aliphatic or cycloaliphatic diols such as propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, butanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol and bis-(hydroxymethyl)-tricyclodecane.
- Also useful for the intended purpose are the poly-(allyl carbonates) polyols, such as tris-(allyl carbonate) of trimethylolpropane and of tris-hydroxyethyl-isocyanurate and pentaerythritol tetrakis-(allyl carbonate).
- These allyl carbonate compounds can be obtained by means of a reaction of transesterification, by reacting diallyl carbonate with the diol or polyol, such as disclosed, e.g., in European patent application Publ. No. 35,304.
- When the process is carried out by means of a transesterification, as the reaction products monomeric bis- or poly-(allyl carbonates) respectively of diols or of polyols, in mixture with the relevant oligomers, as a function of the ratio of the diallyl carbonate reactants to the diol or polyol, are obtained.
-
- R is the diethylene glycol radical, and
- n varies as a function of the ratio of the reactants to each other,
- as reported in the following table.
- More in particular, in this table by ROthe molar ratio of the diallyl carbonate to diethylene glycol in the transesterification is indicated, and the reported percentages, for each individual ratio, represent the percent contents by weight of the monomer (n = 1) and of the oligomers (n > 1) in the reaction mixture.
- A similar behaviour is observed when the transesterification is carried out with the other diols and with the polyols.
- Also those compositions in which the bis-(allyl carbonate) or poly-(allyl carbonate) constituting the (a) component is partially in monomer form, and partially in oligomer form, on condition that the content of oligomer does not exceed about 70% in the mixture, are useful for the purposes of the present invention.
- The preferred (a) components for the purposes of the present invention are diethylene-glycol bis-(allyl carbonate), dimethylol-cyclohexane bis-(allyl carbonate), tris-hydroxyethyl isocyanurate tris-(allyl carbonate) and pentaerythritol tetrakis-(allyl carbonate), possibly partially present in oligomer form, or their mixtures. Also in case of use of mixtures, the total content of the oligomers shall be not higher than the hereinabove specified value.
- The (b) component of the composition is a vinylic ester and is advantageously selected from among vinyl acetate, vinyl pivalate, vinyl ester of Versatic acid, vinil benzoate, vinyl propionate, vinyl adipate and vinyl succinate.
- Most preferred is vinyl acetate. The (b) component of the present invention can be present or, under the above reported proviso, can be absent and the weight ratio of the (a) component to the (b) component can be comprised within the range of from 100:0 to 70:30.
- The (b) component is preferably present in the composition, and the weight ratio of the (a) component to the (b) component is maintained comprised within the range of from 85:15 to 96:4.
- The (c) component of the composition is an organic peroxide which, under the above specified proviso, can be absent. Anyway, it is preferably present in an amount of from 1 to 5 parts by weight per each 100 parts by weight of the total of the (a) and (b) components. The organic peroxides useful for the intended purpose are those which are soluble in the liquid composition, and are capable of generating free radicals within a temperature range of from 30 to 120 C.
- Non-limitative examples of such organic peroxides are diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di-sec.butyl peroxydicarbonate, sec.-butyl-cyclohexyl peroxydicarbonate, tert.-butyl perbenzoate, tert.-butyl perpivalate and benzoyl peroxide.
- More preferably, the (c) component is present in the composition in an amount comprised within the range of from 2 to 4 parts by weight per each 100 parts by weight of the total of the (a) and (b) components.
- The (d) component of the composition is an organic photoinitiator, which is present in an amount comprised within the range of from 0.5 to 4 parts by weight per each 100 parts by weight of the total of (a) and (b) components. The organic photoinitiators useful for the purpose of the invention are those compounds which are soluble in the liquid composition and are capable of generating free radicals under the action of U.V. light.
- Non-limitative examples of such organic photoinitiators are benzyl-dimethyl-ketal, 2-hydroxy-2-methyl-1-phenylpropanone-1, thioxanthone and benzoin ethers.
- The (d) component is preferably present in an amount comprised within the range of from 1 to 3 parts by weight per each 100 parts by weight of the total of (a) and (b) components.
- According to a preferred form of practical embodiment of the present invention,.the polymerizable liquid composition additionally contains small amounts of an organic compound [the (e) component], selected from among those used in the art in order to stabilize the organic polymers to the degrading action of U.V. light. Such stabilizing organic compounds are advantageously selected from among sterically hindered amines, benzophenones and benzotriazoles. The sterically hindered amines are those which are nornally known in the art as "HALS"; a typical example of them is the commercial product TINUVIN 770 by Ciba-Geigy.
- Examples of benzophenones suitable for the intended purpose are 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-octoxy-benzophenone, 2-hydroxy-4-iso-octoxy-benzophenone and 2-hydroxy-4-dodecyloxy benzophenone.
- Examples of triazoles useful for the intended purpose are 2-(3'-tert.-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole, 2-(3',5'-di-tert.-butyl-2'-hydroxy-phenyl)-5-chloro-benzotriazole, and 2-(2 -hydroxy-3 ,5 -di-tert.-amyi-phenyi)-benzotriazoie.
- The present Applicant has surprisingly found that when said (e) component in present in amounts of the order of from 0.05 to 0.15 parts by weight per each 100 parts by weight of the total of (a) and (b) components, it does not have a meaningful influence on the course of the polymerization of the composition, and considerably improves the ageing resistance and the optical characteristics of the so obtained organic glasses.
- The liquid polymerizable composition can additionally contain one or more conventional additives, such as mould-release agents, dyeing agents, pigments are the like, in any case in a total amount not higher than 1% by weight relatively to the weight of the same composition.
- The hereinabove disclosed composition can be used as a protective coating on solid substrates, such as wood (furniture pieces and floors), metals, plastic materials and fabrics. The coating will preferably have a thickness comprised within the range of from 5 to 500 urn. The coated articles show characteristics of scratch resistance, of resistance to solvents, and of high gloss.
- The liquid polymerizable composition is preferably transformed into organic glasses by means of the in- mould polymerization process (the casting process). According to a preferred form of practical embodiment, according to which the (c) component is present, said composition, once poured into the mould, is submitted to a pre-heating, before being treated with U.V. light. The temperature at which the composition is pre-heated can vary as a function of the particular peroxide used, and will be generally comprised within the range of from 40 to 120 C, and preferably of the order of from 70 to 90 C.
- In this way, the polymerization is initiated by the free radicals generated by the decomposition of the initiators contained in the same composition, by thermal effect, and by the treatment with U.V. light.
- By operating according to the process of the present invention, the polymerization times are in any case shorter than about 15 minutes and typically are of the order of a few minutes. The so obtained organic glasses show high optical properties (transparence, absence of colour, low optical distorsion) and good mechanical and thermal properties, as it will be evident from the following experimental examples, which are reported for the purpose of merely exemplifying the present invention without limiting it.
- In said examples, the liquid compositions, comprising the peroxidic initiator and the photoinitiator are prepared, and said compositions are then submitted to polymerization inside glass moulds assembled with a gasket of plasticized poly-(vinyl chloride), which detemines the thickness of the produced organic glass. In particular, flat sheets having a thickness of 1.4 mm and 3.0 mm, and neutral lenses having a thickness of 2 mm are prepared.
- The compositions are polymerized by means of the irradiation with U.V. light emitted by a medium-pressure mercury U.V. lamp of 80 W/cm of power, placed at a distance of 11 cm from the sample to be polymerized. Said sample is conveyed on a conveyor belt at a running speed of 5 metres/minute, and is polymerized by means of a series of repeated exposures on both of its sides, at time intervals of about 5 seconds.
- In some cases, the polymerization with U.V. light is preceded by a heating of a few minutes, so as to increase the temperature of the sample to values of the order of 90° C. The advantages achieved by means of this treatment are of kinetic character (reduction of the exposure times) and in terms of improved optical quality in the obtained organic glasses (lower optical distorsion).
- On the obtained organic glasses the values of the following characteristics are determined.
-
- ■ Refractive index (
- ■ Haze and Transmittance in the visible range (%): measured by means of the Gardner's Hazegard XL-211 (ASTM D-1003)
- 0 Yellow index (YI), defined as:
-
- o Rockwell hardness (M), measured by means of the Rockwell Durometer (ASTM D-785)
- ■ Elastic bending modulus (ASTM D-790)
- ■ Sutherland abrasion resistance.
- The test is carried out on the lenses and consists in submitting the samples to 25 cycles (50 passages) of abrasion by means of a pad of steel wool of 2/0 grade of 5.5 x 7.5 cm of size, loaded with a weight of 630 g. The produced abrasion degree is evaluated by means of the visual observation of the number, the length and the depth of the scratches, as compared to a reference sample on the basis of the homopolymer of diethylene-glycol bis-(allyl carbonate). The resistance to abrasion is expressed by means of a score from a scale of from 0 to 10, with
value 0 being assigned to the completely scratched sample [case of homopolymer of diethylene glycol bis-(allyl carbonate)], assumed as the reference sample, and value 10 being assigned to scratch-free samples. - The intermediate values of from 1 to 9 are assigned on the basis of the percentage of scratches shown by the tested sample relatively to the reference sample. For example, if the sample shows 60% of scratches relatively to the reference sample, its value of abrasion strength is 4, and if is shows 30% of scratches its value is 7, and so on.
- ■ Distorsion temperature under a load of 1.82 MPa (HDT) (ASTM D-648).
- ■ The ageing resistance is determined by means of the exposure of the samples to U.V. light in a Weather-O-Meter (ATLAS), equipped with a Xenon lamp of 6,500 W, with continuous irradiation.
- The temperature on the black reference panel is of 63°C and the relative humidity is of 50%. The ageing resistance is evaluated by determining the Yellow Index after variable times of exposure to U.V. light.
- The examples of polymerization from 1 to 3 report polymerization kinetics which are evaluated by determining the conversion of the allyl unsaturations by means of measurements of densit as a function of the number of passages under the U.V. light lamp.
- Liquid polymerizable compositions are prepared, which contain different amounts of diethylene-glycol bis-(allyl carbonate) and of vinyl acetate.
-
- R = radical of diethylene glycol
- To these compositions dicyclohexyl peroxydicarbonate (DCPD) and 2-hydroxy-2-methyl-1-phenyl- propanone-1 (commerical product DAROCUR 1173) are added.
-
- The values reported in the table for the individual components are parts by weight.
- These compositions are polymerized by casting, to yield flat sheets of 1.4 mm of thickness, by means of irradiation with the U.V. lamp and the degree of conversion of the allyl unsaturations is determined by means of measurements of density as a function of the number of passages under the U.V. lamp. The conversion is expressed as the percent value of the observed increase in density relatively to the total increase in density obtained under conditions of complete polymerization, i.e., when the density of the polymer reaches a constant value.
-
- Polymerizable compositions are prepared which contain dimethylol-cyclohexane bis-(allyl carbonate) (CEDM-BAC), vinyl acetate, DCPD and DAROCUR 1173. Dimethylol-cyclohexane bis-(allyl carbonate) is the product of transesterification of diallyl carbonate with 1,4-dimethylol-cyclohexane in the mutual molar ratio of 4:1, and is a mixture of monomer and oligomers, with a content of oligomers of the order of about 35% by weight.
-
- Polymerizable compositions are prepared which contain tris-hydroxyethyl-isocyanurate tris-(allyl carbonate) (THEIC-TAC), vinyl acetate, DCPD and DAROCUR 1173.
- Tris-hydroxyethyl-isocyanurate tris-(allyl carbonate) is the product of transesterification of diallyl carbonate with tris-hydroxyethyl-isocyanurate in the mutual molar ratio of 12:1, and is a mixture of monomer and oligomers, with a content of oligomers of the order of about 25-30% by weight in the mixture.
-
- Polymerizable compositions are prepared which contain 1,4-dimethylol-cyclohexane bis-(allyl carbonate) (CEDM-BAC of Example 2), diethylene-glycol bis-(allyl carbonate (DEG-BAC), vinyl acetate, DCPD, DAROCUR 1173 and the U.V. stabilizer 2-hydroxy-4-methoxy-benzophenone (commercial product CYASORB UV 9 manufactured by the U.S. Company American Cyanamid).
-
-
- With these compositions neutral lenses of 2 mm of thickness are prepared by means of 30 passages of both of their sides of the hereinabove described U.V. apparatus.
- The U.V. treatment is preceded by a preliminary thermal treatment of 3 minutes in a forced-air- circulation oven at 90 C.
- A the end of the U.V. irradiation, of the total duration of about 5 minutes, at the opening of the mould a perfectly hardened lens is recovered, which is endowed with good optical properties. The characteristics of said lens are reported in Table 8. For comparative purposes, the compositions 13(a) and 14(a), at all similar to Compositions 13 and 14, but without the photoinitiator DAROCUR 1173 are submitted to the hardening process.
-
-
- These compositions are polymerized in the same way as in Example 4 to yield neutral lenses of 2 mm of thickness. The results are reported in Table 10, together with the results relevant to the Compositions 15-(a) and 16(a), polymerized according to the traditional route in the absence of a photoinitiator.
- The polymerizable compositions 17 and 18 are prepared. These compositions are similar to the polymerizable compositions of Example 4, but with pentaerythritol tetrakis-(allyl carbonate) (PE-TETRAKIS) being used in lieu of CEDM-BAC. Said pentaerythritol tetrakis-(allyl carbonate) is the product of transesterification between diallyl carbonate and pentaerythritol in the mutual molar ratio of 24:1, and is a mixture of monomer and oligomers with a content of oligomers of about 20-25% by weight in the mixture.
-
- These compositions are polymerized in the same way as in Example 4 to yield neutral lenses of 2 mm of thickness. The results are reported in Table 12, together with the results relevant to the Compositions 17-(a) and 18(a), polymerized according to the traditional route in the absence of a photoinitiator.
-
-
- The composition No. 21, reported in Example 7, is polymerized to yield flat sheets of 3 mm and 1.7 mm of thickness. By operating under the same conditions as of Example 4, the polymerization is complete and polymerized sheets are obtained, which characteristics similar to those of sheets obtained by means of the traditional thermal route. Such characteristics, relevant to the sheets of 3 mm of thickness, are reported in Table 15. The sheets of 1.4 mm of thickness are used in order to evaluate the ageing resistance, carried out in the Weather-O-Meter.
- The results are reported in Figure of the hereto attached drawing table, in which the Yellow Index is plotted as a function of the exposure time (o-o line).
- By operating in a similar way, but with a composition not containing CYASORB UV 9, the behaviour represented by line o-o is obtained.
-
-
- The viscosity of composition 22 is of 5,500 cSt and the viscosity of composition 23 is of 980 cSt.
- The compositions are applied by means of a film spreader instrument on aluminum sheets or on wooden sheets, and films of about 200µm of thickness are formed.
- The hardening of the so obtained coatings is carried out by means of the exposure, under an inert atmosphere (nitrogen), to the light of a medium-pressure mercury U.V. lamp of 500 W of power, placed at a distance of 15 cm, for a time of 1 minute.
- At the end of the exposure to U.V. light, the coatings result to be completely polymerized, as determined by measurements of density.
- Furthermore, the coatings are free from defects, and are endowed with characteristics of high hardness and high gloss.
Claims (14)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT21009/88A IT1217842B (en) | 1988-06-17 | 1988-06-17 | PROCEDURE FOR THE PREPARATION OF ORGANIC GLASSES |
IT2100988 | 1988-06-17 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0346996A2 true EP0346996A2 (en) | 1989-12-20 |
EP0346996A3 EP0346996A3 (en) | 1991-03-20 |
EP0346996B1 EP0346996B1 (en) | 1994-07-13 |
Family
ID=11175354
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89201532A Expired - Lifetime EP0346996B1 (en) | 1988-06-17 | 1989-06-14 | Process for preparing organic glasses |
Country Status (10)
Country | Link |
---|---|
US (1) | US5128384A (en) |
EP (1) | EP0346996B1 (en) |
JP (1) | JPH0238410A (en) |
KR (1) | KR920009619B1 (en) |
AT (1) | ATE108462T1 (en) |
AU (1) | AU613766B2 (en) |
DE (1) | DE68916712T2 (en) |
ES (1) | ES2056192T3 (en) |
IT (1) | IT1217842B (en) |
MX (1) | MX169951B (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0404888A1 (en) * | 1988-11-18 | 1991-01-02 | Q 2100, Inc. | Plastic lens compositions and apparatus for the production thereof |
EP0458599A2 (en) * | 1990-05-25 | 1991-11-27 | Unilever Plc | Fabric treatment composition |
EP0544497A2 (en) * | 1991-11-25 | 1993-06-02 | Ge Plastics Japan Limited | Delustered thermoplastic resin compositions |
WO1999033887A1 (en) * | 1997-12-30 | 1999-07-08 | Ppg Industries Ohio, Inc. | Partially polymerized mixture of diethylene glycol (allyl carbonate) compounds |
US6730244B1 (en) | 1986-01-28 | 2004-05-04 | Q2100, Inc. | Plastic lens and method for the production thereof |
WO2004090002A1 (en) * | 2003-04-11 | 2004-10-21 | Great Lakes Chemical (Europe) Gmbh | Liquid composition polymerizable into organic glass having good optical and physico-mechanical characteristics |
WO2004090003A1 (en) * | 2003-04-11 | 2004-10-21 | Great Lakes Chemical (Europe) Gmbh | Liquid composition polymerizable into organic glass having a low colouring and good physico-mechanical properties. |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5415816A (en) | 1986-01-28 | 1995-05-16 | Q2100, Inc. | Method for the production of plastic lenses |
US5514214A (en) | 1993-09-20 | 1996-05-07 | Q2100, Inc. | Eyeglass lens and mold spin coater |
US6022498A (en) | 1996-04-19 | 2000-02-08 | Q2100, Inc. | Methods for eyeglass lens curing using ultraviolet light |
US6280171B1 (en) | 1996-06-14 | 2001-08-28 | Q2100, Inc. | El apparatus for eyeglass lens curing using ultraviolet light |
JP4369194B2 (en) * | 2003-09-30 | 2009-11-18 | Hoya株式会社 | Plastic lens and manufacturing method thereof |
ITUA20162086A1 (en) * | 2016-03-29 | 2017-09-29 | Mitsui Chemicals Inc | POLYMERIZED COMPOSITION BASED ON MONOMERI ALLILCARBONATO, A POLYMERIZED PRODUCT OBTAINED FROM SUCH COMPOSITION AND RELATED USES. |
FR3057868B1 (en) * | 2016-10-26 | 2018-10-26 | Arkema France | COMPOSITION BASED ON ALLYLIC MONOMERS AND PEROXIDE (S) FOR THE MANUFACTURE OF ORGANIC GLASSES |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4561951A (en) * | 1982-11-26 | 1985-12-31 | Neckers Douglas C | Method for polymerizing a bis(allyl carbonate) |
US4620954A (en) * | 1985-06-07 | 1986-11-04 | Ciba Vision Care Corp. | Hydrogel from ultraviolet-initiated copolymerization |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2420784C3 (en) * | 1974-04-29 | 1979-02-15 | Siemens Ag, 1000 Berlin Und 8000 Muenchen | Process for the production of molded articles made of polyolefins which are crosslinked by high-energy radiation |
US4623708A (en) * | 1985-03-01 | 1986-11-18 | Coburn Optical Industries, Inc. | Prepolymerization of monomer compositions containing diethylene glycol bis(allyl carbonate) |
IT1207518B (en) * | 1985-12-19 | 1989-05-25 | Enichem Sintesi | LIQUID AND POLYMERIZABLE COMPOSITION FOR THE PRODUCTION OF REPLACED OPTICAL GLASSES. |
IT1223527B (en) * | 1987-12-18 | 1990-09-19 | Enichem Sintesi | POLYMERIZABLE LIQUID COMPOSITION IN ORGANIC GLASSES EQUIPPED WITH LOW WATER ABSORPTION AND HIGH THERMAL STABILITY |
-
1988
- 1988-06-17 IT IT21009/88A patent/IT1217842B/en active
-
1989
- 1989-06-14 EP EP89201532A patent/EP0346996B1/en not_active Expired - Lifetime
- 1989-06-14 AU AU36367/89A patent/AU613766B2/en not_active Ceased
- 1989-06-14 ES ES89201532T patent/ES2056192T3/en not_active Expired - Lifetime
- 1989-06-14 DE DE68916712T patent/DE68916712T2/en not_active Expired - Fee Related
- 1989-06-14 AT AT89201532T patent/ATE108462T1/en not_active IP Right Cessation
- 1989-06-15 MX MX016487A patent/MX169951B/en unknown
- 1989-06-16 JP JP1152458A patent/JPH0238410A/en active Pending
- 1989-06-17 KR KR1019890008366A patent/KR920009619B1/en not_active IP Right Cessation
-
1991
- 1991-08-26 US US07/751,648 patent/US5128384A/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4561951A (en) * | 1982-11-26 | 1985-12-31 | Neckers Douglas C | Method for polymerizing a bis(allyl carbonate) |
US4620954A (en) * | 1985-06-07 | 1986-11-04 | Ciba Vision Care Corp. | Hydrogel from ultraviolet-initiated copolymerization |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6730244B1 (en) | 1986-01-28 | 2004-05-04 | Q2100, Inc. | Plastic lens and method for the production thereof |
EP0404888A1 (en) * | 1988-11-18 | 1991-01-02 | Q 2100, Inc. | Plastic lens compositions and apparatus for the production thereof |
EP0404888A4 (en) * | 1988-11-18 | 1992-03-25 | Ophthalmic Research Group International, Inc. | Plastic lens compositions and apparatus for the production thereof |
EP0458599A3 (en) * | 1990-05-25 | 1992-07-08 | Unilever Plc | Fabric treatment composition |
EP0458599A2 (en) * | 1990-05-25 | 1991-11-27 | Unilever Plc | Fabric treatment composition |
EP0544497A2 (en) * | 1991-11-25 | 1993-06-02 | Ge Plastics Japan Limited | Delustered thermoplastic resin compositions |
EP0544497A3 (en) * | 1991-11-25 | 1993-09-01 | Ge Plastics Japan Limited | Delustered thermoplastic resin compositions |
US5286813A (en) * | 1991-11-25 | 1994-02-15 | Ge Plastics Japan, Ltd. | Melt kneading polycarbonate with compound containing carbon to carbon double bond |
WO1999033887A1 (en) * | 1997-12-30 | 1999-07-08 | Ppg Industries Ohio, Inc. | Partially polymerized mixture of diethylene glycol (allyl carbonate) compounds |
AU739622B2 (en) * | 1997-12-30 | 2001-10-18 | Ppg Industries Ohio, Inc. | Partially polymerized mixture of diethylene glycol (allyl carbonate) compounds |
KR100622174B1 (en) * | 1997-12-30 | 2006-09-07 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Partially polymerized mixture of diethylene glycolallyl carbonate compounds |
WO2004090002A1 (en) * | 2003-04-11 | 2004-10-21 | Great Lakes Chemical (Europe) Gmbh | Liquid composition polymerizable into organic glass having good optical and physico-mechanical characteristics |
WO2004090003A1 (en) * | 2003-04-11 | 2004-10-21 | Great Lakes Chemical (Europe) Gmbh | Liquid composition polymerizable into organic glass having a low colouring and good physico-mechanical properties. |
GB2414736A (en) * | 2003-04-11 | 2005-12-07 | Great Lakes Chemical Corp | Liquid composition polymerizable into organic glass having good optical and physico-mechanical characteristics |
GB2414736B (en) * | 2003-04-11 | 2007-11-14 | Great Lakes Chemical Corp | Liquid composition polymerizable into organic glass having good optical and physico-mechanical characteristics |
Also Published As
Publication number | Publication date |
---|---|
ES2056192T3 (en) | 1994-10-01 |
KR900000401A (en) | 1990-01-30 |
US5128384A (en) | 1992-07-07 |
ATE108462T1 (en) | 1994-07-15 |
EP0346996B1 (en) | 1994-07-13 |
MX169951B (en) | 1993-08-02 |
DE68916712D1 (en) | 1994-08-18 |
KR920009619B1 (en) | 1992-10-22 |
AU613766B2 (en) | 1991-08-08 |
IT1217842B (en) | 1990-03-30 |
DE68916712T2 (en) | 1995-03-02 |
IT8821009A0 (en) | 1988-06-17 |
EP0346996A3 (en) | 1991-03-20 |
JPH0238410A (en) | 1990-02-07 |
AU3636789A (en) | 1989-12-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0346996B1 (en) | Process for preparing organic glasses | |
US4138538A (en) | Process for producing a transparent shaped polymeric product | |
US5702825A (en) | Low yellow index polymer compositions, polymerizable compositions and lenses using said compositions | |
US4912185A (en) | Cross-linkable casting compositions | |
US5373033A (en) | Casting composition | |
EP0114080B1 (en) | Polymerizable liquid composition adapted to produce polymers having outstanding optical and mechanical properties, polymers and articles obtained with said composition | |
EP0201978B1 (en) | Process for the preparation of substitutes for optical glasses and polymerizable liquid composition suitable to that purpose | |
EP3436489B1 (en) | Polymerizable composition based on allyl carbonate monomers, polymerized product obtainable from said composition and uses thereof | |
JP2613785B2 (en) | Liquid polymerizable composition | |
JP2840947B2 (en) | Liquid composition | |
US5545828A (en) | Low yellow index polymer compositions, polymerizable compositions and lenses using said compositions | |
US4835233A (en) | Liquid polymerizable compositions for the production of substitutes for optical glasses | |
EP0241997B1 (en) | Liquid and polymerizable composition suitable for the production of organic glasses endowed with high abrasion strenght | |
US6677420B2 (en) | Polymerisable compositions for making transparent polymer substrates, resulting transparent polymer substrates, and uses thereof in optics | |
US5173552A (en) | Process for the production of thermoformed articles by polymerizing compositions comprising diethylene glycol bis (allylcarbonate) | |
AU683816B1 (en) | Resin composition for polymerization casting and optical material | |
IE860779L (en) | Production of thermoformed articles | |
MXPA00006516A (en) | Partially polymerized mixture of diethylene glycol (allyl carbonate) compounds. | |
EP0947857A2 (en) | Process for providing an optical element and optical element obtainable by such a process | |
JP3527928B2 (en) | Organic glass for optical materials |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE ES FR GB GR LI LU NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE ES FR GB GR LI LU NL SE |
|
17P | Request for examination filed |
Effective date: 19910501 |
|
17Q | First examination report despatched |
Effective date: 19921022 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES FR GB GR LI LU NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19940713 |
|
REF | Corresponds to: |
Ref document number: 108462 Country of ref document: AT Date of ref document: 19940715 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 68916712 Country of ref document: DE Date of ref document: 19940818 |
|
RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: GREAT LAKES CHEMICAL ITALIA S.R.L. |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PUE Owner name: GREAT LAKES CHEMICAL ITALIA S.R.L. |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2056192 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: GR Ref legal event code: FG4A Free format text: 3013050 |
|
EAL | Se: european patent in force in sweden |
Ref document number: 89201532.2 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19950614 Ref country code: AT Effective date: 19950614 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19950615 Ref country code: ES Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES Effective date: 19950615 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19950630 Ref country code: LI Effective date: 19950630 Ref country code: CH Effective date: 19950630 Ref country code: BE Effective date: 19950630 |
|
26N | No opposition filed | ||
BERE | Be: lapsed |
Owner name: GREAT LAKES CHEMICAL ITALIA S.R.L. Effective date: 19950630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19960101 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19950614 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19960229 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL Ref country code: GR Ref legal event code: MM2A Free format text: 3013050 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19960101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19960301 |
|
EUG | Se: european patent has lapsed |
Ref document number: 89201532.2 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 19991007 |